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In-situ Measurement Of Reactive Hydrocarbons At Hohenpeissenberg With Comprehensive Two-dimensional Gas Chromatography (GC×GC-FID): Use In Estimating HO And NO 3

S. Bartenbach, J. Williams, C. Plass-Duelmer, H. Berresheim, J. Lelieveld
Published 2007 · Chemistry

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During a field campaign at the Meteorological Ob- servatory Hohenpeissenberg (MOHp) in July 2004, volatile organic compounds (VOCs) were measured using compre- hensive two-dimensional gas chromatography (GC◊GC). Comparison to routinely made gas chromatography mass spectrometry (GC-MS) measurements showed good agree- ment for a variety of anthropogenic and biogenic ambi- ent VOCs ranging in concentration from below the detec- tion limit (0.1 pmol mol 1 ) to 180 pmol mol 1 . Pronounced diurnal cycles were found for both the biogenic and an- thropogenic compounds, driven for the most part by the daily rise and fall of the boundary layer over the station. For the reactive compounds (lifetimes <2 days), a signif- icant, non-zero dependency of the variability on lifetime was found, indicating that chemistry (as opposed to trans- port alone) was playing a role in determining the ambient VOC concentrations. The relationship was exploited using a single-variate analysis to derive a daytime mean value of HO (5.3±1.4◊10 6 molecules cm 3 ), which compares well to that measured at the site, 3.2±2.3◊10 6 molecules cm 3 . The analysis was extended to the night time data to estimate concentrations for NO3 (1.47±0.2◊10 8 molecules cm 3 ), which is not measured at the site. The feasibility of this ap- proach for environments dominated by emissions of short- lived VOCs to estimate ambient levels of radical species is discussed.
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